Sulfur-curable compositions containing poly-unsaturated compounds as curing promoters



United States Patent SULFUR-CURABLE COMPOSITIONS CONTAINING POLY-UNSATURATED COMPOUNDS AS CURING PROMOTERS .l'ohn Frederick Smith, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Nov. 15, 1962, Ser. No. 238,002

14 Claims. (Cl. 260-415) This invention relates to sulfur-curable, filler-loaded elastomeric composition. More particularly, it relates to sulfur-cured, filler-loaded elastomers and methods for their preparation.

Sulfur-curable a-olefin hydrocarbon copolymers are acquiring increasing importance today in the manufacture of a Wide variety of useful products. For some applications, such as shoe soles and heels, it is desirable that a large proportion of a reinforcing kaolin clay filler be present along with the a-olefin copolymer. Although such compositions can be cured by numerous sulfur-curing systerns, the vulcanizates obtained require a higher modulus and lower compression sets for the contemplated uses. For other applications, such as vent window seals and molded corners on windshield gaskets, it is desirable that a large proportion of a reinforcing carbon black be used to extend the u-olefin copolymer; however, the compression sets at 100 C. of the vulcanizates obtained with the usual sulfur curing systems have left something to be desired. Butyl rubber, likewise, is extended with clays and carbon blacks for many applications and it would be desirable that the vulcanizates obtained from these compositions display a smaller compression set and a higher modulus without the necessity for employing a heat-treatment prior to the curing process. It is known that improved results can be attained, to some extent, if these filled stocks are specially heat-treated prior to incorporation of the curing agent, and it has also been found that this heat-treatment is made more effective if certain promoters are present during the heat-treatment such as the dinitroso, dioxime, and aromatic quinoid compounds. It is, however, quite inconvenient and expensive to carry out the heat-treatment process. to cool the heat-treated stocks before the curing agents can be added lowers the production rate.

It is, therefore, an object of the present invention to provide novel loaded hydrocarbon compositions displaying improved curability. It is a further object to provide novel sulfur-cured, filler-loaded a-olefin and butyl rubber copolymer compositions and methods for their preparation. Another object is to provide such compositions which display improved modulus and a lower compression set. Yet another object is to provide such compositions by a process which obviates the need for an intervening heat-treatment step. Other objects will appear hereinafter.

These and other objects are accomplished in accordance with this invention by a process for preparing a sulfur-cured, filler-loaded elastomeric composition which comprises mixing (I) a normally solid elastomeric copolymer selected from the group consisting of (a) a copolymer of at least one u-monoolefin and at least one nonconjugated hydrocarbon diene of from 5 to 22 carbon atoms, said copolymer having up to about 2 gram-moles The extra time required 3,297,626 Patented Jan. 10, 1967 of carbon-to-carbon double bonds per kilogram, and (b) a copolymer of an isoolefin and a conjugated diene, said isoolefin and diene having from 4 to 14 carbon atoms, and said copolymer having an iodine number of from 1 to about 50; (II) from about 20 to 300 parts of a filler compound per 100 parts of copolymer, (III) up to about 10 parts, per part of copolymer of a monomeric promoter compound selected from the group consisting of di-lower alkenyl esters of unsaturated dicarboxylic acids and N- lower alkenyl substituted amides, said promoter compound having at least 3 sulfur-reactable carbon-to-carbon double bonds per molecule; and (IV) a sulfur-curing system in amounts containing sufficient sulfur to react with said copolymer and said promoter compound; and heating the mixture to effect a cure.

The principal elastomer can be a normally solid elastomeric copolymer of at least one u-monoolefin and at least one non-conjugated hydrocarbon diene.

The a-monoolefins havethe structure RCH=CH wherein R is H or C -C 'alkyl. Representative examples of useful a-monoolefins include: propylene; lbutene; 4methyl-1-pentene; l-pentene; l-hexene; l-heptene; l-octene; l-decene; S-methyl-l-nonene; 5,5-dimethyll-octene; 4-methyl-1-hexene; 4,4-dimethyl-1-pentene; 5- methyl 1 hexene; 4 methyl 1 heptene; 5 methyll-heptene; 4,4-dimethyl-l-hexene; 5,6,6-tnmethyl-1-heptene; l-dodecene; and l-octadecene. The straight chain olefins are preferred.

Representative dienes include open-chain compounds of the formula wherein R is an alkylene radical, R and R are independently selected from the group consisting of hydrogen and alkyl radicals, and R is an alkyl radical' and wherein R to R are so selected that the diene has from about 6 to 22 carbon atoms. Examples of these dienes include: 1,4 hexadiene; 1,9 octadecadiene; 6 methyl 1,5 heptadiene; 7 methyl 1,6 octadiene; 11 ethyl 1,11 -'tridecadiene; 9-ethyl-1,9-undecadiene; 7-ethyl-l,7-nonadiene; 8-propyl-1,8-undecadiene; 8-ethyl-1,8-decadiene; l0-ethyl- 1,9-dodecadiene; 12-ethyl-1,lZ-tetradecadiene; l3-n-butyl- 1,12-heptadecadiene; and 15-ethyl-l,IS-heptadecadiene. Open-chain dienes having two terminal non-conjugated carbon-to-carbon double bonds, e.g., 1,5-hexadiene or 1,4- pentadiene can be used but are less preferred. Representative cyclic non-conjugated dienes include: dicyclopentadiene; 5-alkenyl-substituted-2-norbornene; S-methylene-Z-norbornene; 2-alkyl-2,S-norbornadienes.

Representative examples of copolymers made from these a-monoolefin-s and the above-described non-conjugated dienes and their preparation are described in US. Patents 2,933,480 and 3,000,866 and in French Patents 1,285,090 and 1,302,690. Particularly preferred are copolymers of from about 30 to weight percent ethylene, 30 to 70 weight percent propylene and about 3 to 8 weight percent 1,4-hexadiene or dicyclopentadiene. As previously stated, these copolymers have up to about 2 grammoles of carbon-to-carbon double bonds per kilogram.

These oc-olefin copolymers can be oil extended before they are cured by the present invention. copolymers having Mooney (ML-4/ C.) viscosities of at least 50, preferably higher, and inherent viscosities of 1.8 or

.the' solvent.

above (measured on a 0.1% by weight solution in tetrachloroethylene at 30 C.) have been found to be suitable. The 'oils us'edare p troleiiin oilshavinga flash point of at least about 300 F. and a viscosity-gravity constant in the range of from 0.80 to 1.0, preferably 0.80 to 0.90. The particularly preferred oils have a total nitrogen base and first acidaflin content of not greater than 15% by weight as determined by the Rostler method, described in Industrial and Engineering Chemistry, vol. 41, pages 598 to 608, March 1949. The viscosity-gravity constant is described in the 1958 booklet, A Graphic Method for Selecting Oils Used in Compounding and Extending Butadiene-Styrene Rubbers (Industrial ProductsDepartment, Sun Oil Company, Philadelphia, Pennsylvania, 1958). Representative oils include-paraffinic oils, naphthenic, relatively aromatic, and aromatic oils. The petroleum oil can be introduced into the copolymer any time after the polymerization reaction is finished. The petroleum oil can be added to the solution, the resulting mixture obtained being pumped to a drum dryer to remove Alternatively, the petroleum oil can be into alumina in the clay is in the neighborhood of 2:1, the

value of kaolinite itself.

troduced at thenip of the drum dryer along with the polymer solution. If desired, petroleum oil can be introduced into the dried copolymer stock in a Banbury The principal physical characteristics of a kaolin clay which are preferred for use in the present invention are: (1) a specific gravity of about 2.60; (2) a 325-mesh screen residue below about 3.5%, preferably below about 0.35%; (3) absorbed moisture content not above about to 1%; (4) a particle size distribution wherein at least about 55% by weight of the particles are two microns or less in diameter; and (5) a pH (in water) of about 4.4 to 7.0, although specially prepared and treated clays may show pH values of 8.0 or higher.

Representative hard and soft kaolins contain (by weight): 44 to 46% silica; 37.5 to 39.5% alumina; 0.5 102.0% iron oxide; and 1 to 2% titanium dioxide; the ignition loss of these representative clays i's-13.9 to 14.0% by weight. Clays are more particularly described in-the following publicationsz' Compounding Ingredients for Rubber, third edition, 1961, Cuneo P'ressof New England,

Cambridge, Mass, compiled. by the editors, of Rubber World, 630 Third Avenue, .New. York- 17, New York; Kaolin Clays and Their Industrial Uses, J. M. Huber Corp,' New York, New York, secondedition,1955;.India those skilled in the art. A detailed view of the major petroleum oils is given in the article entitled Hydrocarbon Composition of Rubber'Process Oils by S. Kurtz, Jr., and C. C. Martin, India Rubber World Co.,12 6 No. 4, July 1952, page 495 onward. 2'

Butyl rubbers suitable for use as the principal elastomer in the present invention and closely related-isoolefin copolymer compositions .are moreparticularly described in US. Patent 2,822,342. The isoolefin has 4 to 14 carbon atoms inclusive; the preferred isoolefin is isobutylene.

The multi-olefin has from 4 to 14 carbon atoms inclusive I per molecule and is preferably a conjugated vdiolefin having from 4 to 8 carbon atoms per molecule such as isoprene, butadiene and the like. The preferred copolymers made from isobutylene have an average Standinger molecular weight number within the range between a 20,000 and 200,000 and a Wijs iodine number of from about 1 up to 50. The correspondingly related S-minute Mooney viscosity values of these copolymers is at least 15. The particularly preferred copolymer contains 95 isoprene monomer units by weight, and has the molecular weights and iodine numbers specified above. The preparation of these copolymers is described in greater detail on lines 13 to 75 of column 4 and lines 1 through 75 of column 5 of US. Patent 2,822,342.

The filler compound of the present invention is preferably a kaolin clay or carbon black. Any kaolin clay which is conventionally used for reinforcing elastomers can be employed to make the mixtures of the present invention. the range of 2 microns. The finer the particle size, the better the filler responds in giving an improved vulcanizate. It is not critical whether these kaolin clays are residual or sedimentary in origin; they can be pro- .99.5% of isobutylene monomer units and 5 to 0.5% of a In general, these clays have particle sizes in duced by any conventional process such as the dry process titanium, calcium, magnesium, potassium, sodium, and

occasionally manganese; in kaolinites minor proportions of hydrated aluminum silicate minerals other than kaolinite may be present; In' general, the molar ratio of silica Rubber World, vol. 118, No. 6, NewYork, September 1948, pages,.793-795; Clays, Their Occurrence, Properties and Uses, H. Ries, third edition, John Wiley & Sons, II1c., New York, 1927; The,Chemistry and Physics of Clays and Other Ceramic Materials, A. B. Searle and R. W. Grimshaw, third edition, Interscience Publishers, Inc., New York, 1959; Preliminary-Reports Reference Clay Materials, American Petroleum Institute Research Project 49, Columbia University," New York, January, 1951, and X-Ray Identification and Crystal Structures of Clay Ma- -terials, edited by Brindley, London, 1951.

Whencarbon black is to be used channel and furnace process. blacks are preferred. Stocks containing the former filler are slightly slower curing. Thus any'ofthe channel blacks such as EPC, MPG, HPC, CC can be used. SAF furnace black is anexcellent reinforcingagent; other furnace blacks such. as SRE, HMF, CF, :HAF,- and FF can also be satisfactorily used. Thermal carbons can be employed but provide a lower order of reinforcement..'

' About 20 to 300 partsof filler are used=per parts of copolymer.; Whencarbon black-is used the amounts are frequently from 20 -to- 80 parts; when-kaolin clay is the filler the amounts are frequently in the range of 80 to parts.

The promoter is a monomeric compound selected from the group consisting of di-lower alkenyl esters of unsaturated dic'arboxylic acids and N-lower alkenyl substituted amides; the compound must have at least 3 sulfur-reactable carbon-to-carbon double bonds per molecule. Suitable promoters include: diallyl esters of unsaturated dicarboxylic acids, e.g., diallyl fumerate, diallyl maleat'e and diallyl itaconate; N,N liallyl amides of anu'nsaturated monocarboxylic acid, e.g., N,N-diall'yl acrylamide and N,N-diallyl ,methacrylamide; and N,N,N,N-tetraallyl succinamide and N,N,N',N-tetraallyl terephthalamide. Other unsaturated amides can be made by reacting unsaturated amines, e.g., diallyla'mine, with bis-acid halides such as terephthaloyl chloride.

The proportion of the polyunsaturated monomeric promoter compound to the elastomer shouldbe selected so that there is at least about 0.05 gram-mole of carboncarbon double bonds in the'promoter for every grammole of carbon-carbon double bonds in the elastomer. Otherwise vulcanizate properties tend to fall off,-particularly the modulus and the compression set. The preferred ratios have' values ranging from about 0.1 to about 1. Proportions giving a ratio above 1, e.g., 1.9,'- are usable but are not necessary and increase the sulfur requirement needlessly. In order to avoid adversely affect ing the vulcanizate properties of the elastomer, it is desirable to avoid using too high a proportion by weight of the promoter compound. Those skilled in'the art can determine the exact limit for each promoter compound employed by emipirical experiments; however, in general, it is preferred to limit the weight to about that of the elastomer with frorn'2 to 3% being particularly preferred.

In operating the present invention, the cure promoter system is mixed with the principal elastomer stock at any time before curing begins. Although the order of addition is not important, it is essential that both the polyunsaturated promoter compound and the sulfur for its carbon-to-carbon double bonds be present. This frequently calls for 40% or more sulfur than would be used for the elastomer alone. If this additional sulfur is missing, the polyunsaturated promoter compound will consume sulfur needed for curing the elastomer itself and lead to an inferior vulcanizate. Mixing of the components of the curable composition is carried out in the conventional manner using rubber roll mills, Banbury mixers, and the like. In order to avoid remature scorch, it is preferred to mix at temperatures in the range 75 to 100 F., well below the core temperature.

The compositions of the present invention can be very readily cured with sulfur to give outstanding vulcanizates. Any of the procedures familiar to those skilled in the processing of natural rubber, butadiene/styrene rubber and butyl'ru'bber are suitable. It is preferable to use a combination of sulfur, a metal oxide, and a vulcanization accelerator. In general, about 0.2 to 3.5 parts of sulfur are used per 100 parts by weight of copolymer; it is to be understood that larger or smal er concentrations may be used when deemed desirable. Zinc oxide and cadmium oxide are the preferred oxides; zinc oxide is particularly preferred because it is more efficient, lower in cost, and is less hazardous to use. The concentration of the metal oxide is important since it, in conjunction with sulfur and accelerator, controls the ultimate state of cure. At concentrations of 3 to 10 parts by weight per 100 parts by weight of elastomer, the rate and state of cure are very satisfactory as indicated by modulus, compression set, and elongation. Concentrations above 10 parts are unnecessary. Concentrations below 3 parts are less satisfactory for developing and maintaining adequate vulcanizate properties. The most active accelerators include Z-mercaptobenzothiazole, thiuram sulfides, dithiocarbamates and their simple derivatives. Of the three classes, the thiuram sulfi 165 and dithiocarbamates are generally preferred because they produce rapid curing without attendant scorching and develop and maintain maxi-mum physical properties even on extended curing cycles. For many uses, however, Z-mercapto-benzothiazole and its derivatives, alone or in combination with thiurams or dithiocarbamates provide adequate acceleration with processing safety. Representative accelerators include: tetramet-hyl thiuram monosulfide; tetr-amethyl thiuram disulfide; tellurium monosulfide; tetramethyl thiuram disulfide; tellurium diethyldithiocanbamate; the zinc salt of dimethyl dithiocarbamic acid; the piperidine salt of pentamethylene dithiocarbamic acid; Z-mercaptothiazoline; Z-mercaptothiazole; N,N-diethyl-thiocarbamyl-Z-mercaptobenzothiazole; and 2,2'-dithiobis benzothiazole. Unlike natural rubber and styrene-butadiene rub'ber, the presence of a fatty acid is not necessary for the vulcanization of the OC- olefin copolymers. In fact, their vulcanization is inhibited by the presence of relatively weak carboxylic acids if used in excessive amounts. At low concentrations (0.25 to 1.0 part by weight of copolymer), stearic acid is very useful as a release agent for heavily loaded stocks. Vulcan zation is accomplished by heating the compounded stock (usually in a mold) at a temperature of about 266 F. (130 C.) to 356 F. (180 C.) for a period ranging from about 5 minutes to several hours; it is often preferred to cure the stock at 320 F. (160 C.) for about 20 to 30 minutes. Steam cures can be employed as well. Representative pressures can range from 60 to 225 lb./ sq. in. steam and representative times can range from about 30 seconds to 30 minutes. The preferred steam cure is about 30 seconds at 225 lb./sq. in. steam pressure. The state of cure is best determined by extension modulus at 300% elongation.

It is to be understood that various modifications of the sulfur curing procedure may be employed depending upon the stock. Various procedures and modifications of sulfur curing are more particularly described in Encyclopedia of Chemical Technology, Kirk and Othrner, published by Inter-Science Encyclopedia, Inc., New York, 1953, 11, pp. 892927; Principles of High-Polymer Theory and Practice, Schmidt and Marlies, published by McGraw- Hill Book Co., New York, 1948, pp. 556566; Chemistry and Technology of Rubber, Davis and Blake, published by Reinhold Publishing Corp., New York, 1937, chapter 6; Introduction to Rubber Technology, edited by M. Morton, Reinhold Publishing Corp., New York, 1959, pp. 93-129; The Applied Science of Rubber, edited by W. J. S. Naunton, Edward Arnold Ltd., London, 1961, pp. 346- 413, 9921099.

The invention will now be described in and by the following examples of certain preferred embodiments wherein parts and percentages are by weight unless otherwise specified.

Example I A sulfur-curable ethylene hydrocarbon copolymer is prepared in accordance With the general directions described in US. Patent 2,933,480 and consists of the following monomer units by weight: 56.5% ethylene, 40.0% propylene, and 3.5% 1,4-hexadiene. The copolymer exhibits a Mooney viscosity (ML4/100 C.) of 90.

The filler employed is an air-floated hard kaolin clay (commercially available from the J. M. Huber Corporation, New York, New York, as Suprex clay) containing 44 to 46% silica, 37.5 to 39.5% alumina, 1.5 to 2.0% iron .oxide, and 1 to 2% titanium dioxide by weight, the ignition loss being 13.9 to 14.2 by weight. The maximum moisture content is 1% by weight and the pH (in water) is 4.5 to 5.5. This clay has a specific gravity of 2.60, a 325-mesh screen residue of 0.17% by weight and the following particle size distribution (by Weight): greater than 10 microns, 0.1%; 5 to 10 microns, 2.8%; 4 to 5 microns, 1.5%; 3 to 4 microns, 2.3%; 2 to 3 microns, 3.4%; 1 to 2 microns, 9.0%; 0.5 to 1.0 micron, 19.0%; and 0 to 0.5 micron, 61.9%.

Four stocks are compounded on a rubber roll mill at a temperature between F. and F. containing parts of ingredients according to the following recipe.

Component: Parts by weight Ethylene/propylene/ 1,4-

hexadiene copolymer 100 Kaolin clay Naphthenic petroleum oil 1 40 Zinc oxide 5 Tetraallyl terephthalamide (see table below). Tetramethyl thiuram monosulfide 2.65 Z-mercaptobenzothiazole 0.53 Sulfur 3.31

1 Flash point 445 F. Sum of N-bases and first acidaffins 1.5% second acidaffins 28.3%; parafiins 70.2%. Viscositvgravity constant 0.834.

The stocks thereby obtained are cured for 5, 10, and 30 minutes in a press at 320 F, C.), the vulcanizates giving the following representative data at 25 C.:

IA 18 IC ID Tctrnallyl terephthalamide 1. 32 2. 65 3. 98 Cure: /320 F.:

300%Modulus, p.s.i 400 450 340 340 Tensile Strength, p.s.i 1, 340 1,200 980 1, 710 Extension at Break, percent 800 1. 000 1, 000 900 I Flash point 445 F. Sum of N-buses and first acidatfins 1.5%; second acidalfins 28.3%; pnmllins 70.2%. Viscosity-gravity constant 0.834.

IA IB IC ID Cure: /320 F.:

300% Modulus, p.s.i 000 580 510 430 Tensile Strength, p.s.i 1, 550 1, 370 1. 301 I2, 000 Extension at Break, percent 850 905 990 S40 Cure: Sty/320 F.:

300% Modulus, p.s.i 800 760 030 000 Tensile Strength, p.s 1, 020 1, 450 1,320 1,731 Extension at Break, percent 045 720 805 070 Stock ID is a control containing no promoter com- Component: Pans by Weight position Ethylene/ propylene/1,4-hexad1ene copolyrner 100 From the above data it appears that the modulus can gi ig T 33 be substantially improved by employing the monomeric P m t m d t M b l w promoter compound. romo e r compoun (see a e e O Zmc oxide 5 Example 11 Zinc dimethyldithiocarbamate 2- Example I is repeated except that the promoter comrilfercaptobenzothlazole LI 111 pound is changed to tetraallyl succinamide.

The stocks thereby obtained are cured in a press at These stocks are then cured for 20 minutes at 320 F.

in a press. The following representative data are obtained at 25 C.:

Additive Phr. 300 B 15 111K None 0 040 2,020 000 320 F. (160 C.) for 5, 10 and minutes. The fol- E l V lowing representative data are obtained at 25 C.:

11A HE 110 Tctraallyl succinalnide 1. 32 2. 65 3. 98 Cure: 5/320 F.:

300% Modulus, p.s.i 500 550 460 Tensile Strength, p.s 1,350 1, 320 1,200

Extension at Break, percent .1 970 4 1, 000 Cure: 10/320 F.:

300% Modulus, p.s.i 660 670 580 Tensile Strength, psi 1, 500 1, 420 1, 410

Extension at Break, percent 800 820 955 Cure: 30/320 F.:

300% Modulus, p.s.i 880 950 750 Tensile Strength, p.s.i 1, 500 1.370 1,380

Extension at Break, percent 020 540 790 The modulus of stocks prepared according to this invention (11AC) are greatly improved over that obtained 'when the promoter is omitted.

(See Example I stock Example III A butyl rubber is selected consisting of 97 weight percent isobutylene monomer units and 3 weight percent isoprene monomer units. I

Two stocks are compounded on a rubber roll mill at a temperature between F. and 100 F. according to the following general recipe.

These stocks are then vulcanized for 10 to 30 minutes at 320 F. in a press. The vulcanizates obtained displayed the following stress-strain properties at 25 C.:

IVA IVB Diallylacrybunide 1 0 Cure: 10I320 F.:

300% Modulus, p.s.i 050 400 Tensile Strength, p.s.i 1,375 1, 550

Elongation at Break, percent 660 680 Cure: 30/320 F.:

300% Modulus, 1.5 i 775 600 Ten-tile Strength, p. 1, 100 1, (300 Elongation at Break, perccn 480 440 It is clear that stock IVA prepared according to this invention has a modulus greatly improved over control stock IVB containing no promoter compound.

It has been found that the minimum number of 3 sulfur-reactable carbon-to-carbon double bonds in the promoter is critical. If, for example 0.5 or 1.0 phr. of diallyl disulfide (containing only 2 double bonds per molecule) is substituted for any of the promoters of the invention in Example III, the resulting vulcanizate shows no improvement in modulus over control sample IIIK containing no promoter.

In the foregoing examples vulcanizate properties are measured in accordance with the following procedures.

Property: ASTM method Stress-strain D412-51T. Compression set D395-55, Method B.

A distinct advantage of the promoters of the present invention is that they obviate thet necessity for carrying out the heat-treatment step when curing stocks containing a kaolin clay. Results are obtained which are com parable to those gained by the use of heat-treatment in combination with butyl rubber type heat-treatment promoters. In a similar fashion, the compression set of vulcanizates made from mixtures of this copolymer with carbon black are as good as those of vulcanizates of this copolymer which have undergone a preliminary heattreatment of the black stock with paraquinone dioxime.

The a-olefin compositions of the present invention possesses excellent ozone resistance and weatherability (that is, freedom from cracking and crazing) which makes them especially suitable for black stock applications such as hose, windshield blades and the like. The oil extended u-olefin compositions are characterized by exceptionally improved processing behavior which makes them very easy to calender and extrude. The a-olefin compositions loaded with clay can be employed in the preparation of shoe soles and heels and a wide variety of molded articles. The uncured but compounded compositions are not affected by moisture and can be stored for lengthy periods before shaping and vulcanization.

The improved butyl stocks are useful in making inner tubes, tires, fabric impregnation and coating, air bags, cements, adhesives and materials for electrical applications.

What is claimed is:

1. A process for preparing a sulfur-cured, filler-loaded elastomeric composition which comprises mixing (I) a normally solid elastomeric copolymer selected from the group consisting of (a) a copolymer of at least one amonoolefin of the formula RC=CH where R is selected from the group consisting of hydrogen and C -C alkyl radicals and at least one non-conjugated hydrocarbon diene of from to 22 carbon atoms, said copolymer having up to about 2 gram-moles of carbon-to-carbon double bonds per kilogram, and (b) a copolymer of an isoolefin and a conjugated diene, said isoolefin and diene having from 4 to 14 carbon atoms, and said copolymer having an iodine number of from 1 to about 50; (II) about 20 to 300 parts of a filler compound per 100 parts of copolymer; (III) a monomeric curing promoter compound selected from the group consisting of di-allyl esters of unsaturated dicarboxylic acids and N-allyl substituted amides, said promoter compound having at least 3 sulfurreactable carbon-to-carbon double bonds per molecule and being present in an amount to give about 0.05 to 1.9 gram-moles of carbon-carbon double bonds in the promoter for every gram-mole of carbon-carbon double bonds in said copolymer; and (IV) a sulfur-curing system in amounts containing about 0.2 to 3.5 parts of sulfur per 100 parts by weight of said copolymer to react with said copolymer and up to 40% additional sulfur to react with said promoter; and heating the mixture to effect a cure.

2. A process as defined in claim 1 wherein said copolymer (a) is a copolymer containing from about 30 to 70% ethylene units, about 30 to 70% propylene units and up to 8% of at least one non-conjugated diene of from about 6 to 22 carbon atoms.

3. A process as defined in claim 1 wherein said copolymer (b) is a copolymer of at least isobutylene and from about 0.5 to 5% of a conjugated diolefin having from 4 to 8 carbon atoms.

4. A process as defined in claim 1 wherein said monomeric promoter compound is a diallyl ester of an unsaturated dicarboxylic acid.

5. A process as defined in claim 1 wherein said monomeric promoter compound is an N,N-diallyl amide of an unsaturated monocarboxylic acid.

6. A process as defined in claim 1 wherein said monomeric promoter compound is an N,N,N',N-tetraallyl diamide of a dicarboxylic acid.

7. A process as defined in claim 1 wherein said filler compound is kaolin clay.

8. A sulfur-curable, filler-loaded elastomeric composition comprising (I) a normally solid elastomeric copolymer selected from the group consiting of (a) a copolymer of at least one a-monoolefin of the formula RC CH where R is selected from the group consisting of hydrogen and C C alkyl radicals and at least one non-conjugated hydrocarbon diene of from 5 to 22 carbon atoms, said copolymer having up to amout 2 gram-moles of carbonto-carbon double bonds per kilogram, and (b) a copolymer of an isoolefin and a conjugated diene, said isoolefin and diene having from 4 to 14 carbon atoms, and said copolymer having an iodine number of from 1 to about 50; (11) about 20 to 300 parts of a filler compound per parts of copolymer; (III) a monomeric curing promoter compound selected from the group consisting of di-allyl esters of unsaturated dicarboxylic acids and N- allyl substituted amides, said promoter compound having at least 3 sulfur-reactable carbon-to-carbon double bonds per molecule and being present in an amount to give about 0.05 to 1.9 gram-moles of carbon-carbon double bonds in the promoter for every gram-mole of carboncarbon double bonds in said copolymer; and (IV) a sulfur-curing system in amounts containing about 0.2 to 3.5 of sulfur per 100 parts by weight of said copolymer to react with said copolymer and up to 40% additional sulfur to react with said promoter.

9. A composition as defined in claim 8 wherein said copolymer (a) is a copolymer containing from about 30 to 70% ethylene units, about 30 to 70% propylene units and up to 8% of at least one non-conjugated diene of from about 5 to 22 carbon atoms.

10. A composition as defined in claim 8 wherein said copolymer (b) is a copolymer of at least 95% isobutylene and from about 0.5 to 5% of a conjugated diolefin having from 4 to 8 carbon atoms.

11. A composition as defined in claim 8 wherein said monomeric promoter compound is a diallyl ester of an unsaturated dicarboxylic acid.

12. A composition as defined in claim 8 wherein said monomeric promoter compound is an N,N-diallyl amide of an unsaturated monocarboxylic acid.

13. A composition as defined in claim 8 wherein said monomeric promoter compound is an N,N,N',N'-tetraallyl diamide of a dicarboxylic acid.

14. A composition as defined in claim 8 wherein said filler compound is kaolin clay.

References Cited by the Examiner UNITED STATES PATENTS 2,933,480 4/ 1960 Gresham et al 26041 2,977,345 3/1961 Fischer et al. 26079.5 3,011,995 12/1961 Smith 260-41 MORRIS LIEBMAN, Primary Examiner.

K. B. CLARK, Examiner.

J. S. WALDRON, Assistant Examiner. 

1. A PROCESS FOR PREPARING A SULFUR-CURED, FILLER-LOADED ELASTOMERIC COMPOSITION WHICH COMPRISES MIXING (I) A NORMALLY SOLID ELASTOMERIC COPOLYMER SELECTED FROM THE GROUP CONSISTING OF (A) A COPOLYMER OF AT LEAST ONE AMONOOLEFIN OF THE FORMULA R-C=CH2 WHERE R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND C1-C16 ALKYL RADICALS AND AT LEAST ONE NON-CONJUGATED HYDROCARBON DIENE OF FROM 5 TO 22 CARBON ATOMS, SAID COPOLYMER HAVING UP TO ABOUT 2 GRAM-MOLES OF CARBON-TO-CARBON DOUBLE BONDS PER KILOGRAM, AND (B) A COPOLYMER OF AN ISOOLEFIN AND A CONJUGATED DIENE, SAID ISOOLEFIN AND DIENE HAVING FROM 4 TO 14 CARBON ATOMS, AND SAID COPOLYMER HAVING AN IODINE NUMBER OF FROM 1 TO ABOUT 50; (II) ABOUT 20 TO 300 PARTS OF A FILLER COMPOUND PER 100 PARTS OF COPOLYMER; (III) A MONOMERIC CURING PROMOTER COMPOUND SELECTED FROM THE GROUP CONSISTING OF DI-ALLYL ESTERS OF UNSATURATED DICRBOXYLIC ACIDS AND N-ALLYL SUBSTITUTED AMIDES, SAID PROMOTER COMPOUND HAVING AT LEAST 3 SULFURREACTABLE CARBON-TO-CARBON DOUBLE BONDS PER MOLECULE AND BEING PRESENT IN AN AMOUNT TO GIVE ABOUT 0.05 TO 1.9 GRAM-MOLES OF CARBON-CARBON DOUBLE BONDS IN THE PROMOTER FOR EVERY GRAM-MOLE OF CARBON-CARBON DOUBLE BONDS IN SAID COPOLYMER; AND (IV) A SULFUR-CURING SYSTEM IN AMOUNTS CONTAINING ABOUT 0.2 TO 3.5 PARTS OF SULFUR PER 10 PARTS BY WEIGHT OF SAID COPOLYMER TO REACT WITH SAID COPOLYMER AND UP TO 40% ADDITIONAL SULFUR TO REACT WITH SAID PROMOTER; AND HETING THE MIXTURE OF EFFECT A CURE. 